Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components

Definitions

• PMDA pyromellitic dianhydride
• DADE 4,4′-diaminodiphenyl ether
• BPDA biphenyltetracarboxylic dianhydride
• DAT 2,4-diaminotoluene
• Solvent-soluble highly heat-resistant polyimides can also be produced by using benzophenone tetracarboxylic dianhydride (called BTDA) in place of BPDA. Similar solvent-soluble polyimides can also be produced by using 3,5-diaminobenzoic acid (hereinafter referred to as DABz) in place of DAT.
• BTDA benzophenone tetracarboxylic dianhydride
• DABz 3,5-diaminobenzoic acid
• KAPTON consists of pyromellitic dianhydride (PMDA) and 1,4-diaminodiphenyl ether (DADE).
• Tg glass transition temperature
• Tm thermal decomposition onset temperature
• a polyimide film called “Upilex” manufactured by Ube Industries, Ltd. in 1980 is a heat-resistant film consisting of biphenyltetracarboxylic dianhydride (BPDA) and 1,4-diaminobenzene and having Tg>500° C. and Tm>550° C. (non-patent document 1).
• BPDA biphenyltetracarboxylic dianhydride
• 1,4-diaminobenzene 1,4-diaminobenzene and having Tg>500° C. and Tm>550° C.
• KAPTON and Upilex are less soluble in organic solvents, and they are polymerized in anhydrous solvents at low temperatures to synthesize a polyamic acid, which is then cast and heated to form a polyimide film.
• Polyamic acids readily decompose in water so that they are poor storage stability. Polyamic acids are difficult to modify because they undergo rapid exchange interaction to form random copolymers when other components are added.
• Toluene sulfonic acid was used as a catalyst (patent document 2: A. Berger, U.S. Pat. No. 4,011,297 (1979), U.S. Pat. No. 4,359,572 (1983)).
• Polyimide copolymers consisting of PMDA and DADE are less soluble in solvents.
• Solvent-soluble four-component polyimides (polyimides consisting of PMDA-DADE-BPDA-DAT) were synthesized via specific imide oligomer intermediates by adopting a novel three-step polycondensation process.
• the first step of polycondensation reaction involves reacting 1 mole of BPDA and 2 moles of DADE (component containing 6 benzene rings) to form an imide oligomer, and the second step reaction involves reacting 4 moles of PMDA and 2 moles of DAT (component containing 6 benzene rings) to synthesize a primary intermediate (called 6,6-polyimide oligomer). Finally, the remaining components are added to complete polycondensation.
• the present invention mainly provides the following two types of polyamides.
• the endpoint of the reaction is determined by measuring the molecular weight by GPC.
• the thermal decomposition onset temperature was 500° C. or more, and no glass transition temperature was observed in a test range up to 430° C.
• Four-component solvent-soluble polyimides are produced by using DABz in place of DAT (variation of (i) or (ii) above). Thermal analysis shows that a weight loss began around 430° C., and that the thermal decomposition onset temperature rose to 540° C.
• a catalyst based on lactone equilibrium was developed. It consists of a mixture of ⁇ -valerolactone and pyridine or ⁇ -valerolactone and N-methylmorpholine, which achieves equilibrium by forming an [acid][base] system in the presence of water and returns to [lactone] and [base] when water is removed from the system (formula 1). [ ⁇ -valerolactone]+[pyridine]+[water] ⁇ [acid] + [base] ⁇ [Formula 1]
• Imidation reaction takes place by adding small amounts of ⁇ -valerolactone and pyridine or ⁇ -valerolactone and N-methylmorpholine into the reaction system, and heating it at 180° C.
• [Acid] + [base] ⁇ is produced by the [water] generated at an early step of the reaction to promote the imidation reaction.
• the water produced during the reaction is removed from the reaction system by azeotropic distillation with toluene contained in the system.
• the reaction system approaches an anhydrous state and the [acid] + [base] ⁇ is separated into [ ⁇ -valerolactone] and [pyridine] and removed from the system.
• a high-purity polyimide copolymer is obtained.
• Solvent-soluble multicomponent block-copolymerized polyimides are produced by sequential polycondensation reactions.
• Four-component block-copolymerized polyimides are produced by the formula below:
• a 1 and A 2 represent acid dianhydrides, and B 1 and B 2 represent aromatic diamines.
• the PMDA-DADE-PMDA component and DADE-PMDA-DADE component are less soluble in solvents. Thus, it was necessary to synthesize block copolymerized polyimides free from these insoluble components.
• 6,6-polyimide copolymers are solvent-soluble polyimide resins showing good storage stability. They can be coated on metal surfaces to form composite materials or used in copper substrates. Modified polyimides can be used for electrodeposition or as adhesives.
• They can be cast/heated into films, which can be widely used as highly heat-resistant films in electric/electronic components, transport aircraft materials, semiconductor materials, etc.
• TeflonTM can be used as medical materials, construction materials, high-temperature materials for domestic uses (e.g., iron soleplates, inner walls of pans, inner walls of microwave ovens), substitutes for TeflonTM by capitalizing on advantages of the new preparation process, high performance quality and low-cost products.
• the first step polycondensation reaction is an imidation reaction in which 2 moles of DADE and 1 mole of BPDA are heated at 180° C. in an organic polar solvent in the presence of an acid catalyst to produce an oligomer having diamine at both ends (formula 5).
• the water produced during the reaction is removed from the system by azeotropic distillation with toluene. 2DADE+BPDA ⁇ (DADE-BPDA-DADE) oligomer [Formula 5]
• the primary intermediate oligomer is a reaction product of components each containing 6 benzene rings in the first step reaction and the second step reaction (formula 8).
• the primary intermediate oligomer is called 6,6-polyimide to distinguish it from other polyimide products because the components added for the first step reaction and the second step reaction each contain 6 benzene rings.
• a 6,6-imide segment is generated, which is combined with a (BPDA+PMDA+3DAT) component and heated with stirring to give a solvent-soluble polyimide copolymer in the third step.
• the first step reaction involves reacting a (BPDA+2DADE) component at 180° C. for 1 hour in an organic solvent in the presence of a catalyst. Then, the second step reaction involves adding a (4PMDA+2DAT) component at room temperature and stirring the mixture to produce a 6,6-imide segment (BPDA+2DADE) (4PMDA+2DAT).
• BPDA+2DADE 4,PMDA+2DAT
• a (BPDA+PMDA+3DAT) component is added to this solution, and the mixture is heated at 180° C. with stirring to give a solvent-soluble polyimide copolymer.
• the first step reaction involves reacting a (BPDA+2DADE) component in an organic solvent at 180° C. for 1 hour to produce an imide oligomer.
• polyimide copolymers having a (BPDA):(DADE):(PMDA):(DAT) molar ratio of 2:2:m:m (where m is an integer of 3, 4 or 5.) are obtained.
• BPDA BPDA
• DEA dihydroxybenzoic acid
• PMDA cyclopentadiene
• DAT dihydroxybenzoic acid
• a part of each polyimide solution was cast on a glass plate and heated in an IR heater at 90° C. for 1 hour and 210° C. for 1 hour into a polyimide film, which was then tested by thermal analysis.
• the thermal decomposition onset temperature was 500° C. or more, and no glass transition temperature could be observed in a test range up to 430° C.
• Solvent-soluble polyimides having similar compositions are produced by using benzophenone tetracarboxylic dianhydride (BTDA) in place of BPDA in the synthetic reaction.
• BTDA benzophenone tetracarboxylic dianhydride
• polyimides having a (BTDA):(DADE):(PMDA):(DAT) of molar ratio 2:2:m:m (where m is an integer of 3, 4 or 5.) are produced.
• Thermal analysis of these polyimides showed T m of 500° C. or more and no T g in a test range up to 430° C.
• Polyimides using BTDA in place of BPDA show higher M W (weight average molecular weight)/M N (number average molecular weight) ratios, suggesting that they are partially crosslinked. They can be used as copper substrates or composite polyimide materials because of their good adhesiveness.
• Diaminotoluene having the structure below:
• DAT can be replaced by 3,5-diaminoacetic acid (DABz) in the synthetic reactions of the (PMDA-DADE-BPDA-DAT) series and (PMDA-DADE-BTDA-DAT) series of polyimides using similar experimental procedures.
• DABz 3,5-diaminoacetic acid
• DAT in the second step may be replaced by DABz or DAT in the third step may be replaced by DABz.
• Thermal analysis shows a weight loss around 440-450° C. in DABz-containing polyimide copolymers, i.e., (PMDA-DADE-BPDA-DABz) and (PMDA-DADE-BTDA-DABz) systems. This suggests that decarbonation reaction occurs.
• polyimide copolymers can be used as polyimide coatings by cathodic electrodeposition. They can also be used as composite materials because of their good adhesiveness.
• the molecular weights of DABz-containing polyimide copolymers could not be determined by GPC in dimethylformamide.
• the methyl group of diaminotoluene is adjacent to an amino group to cause molecular distortion when a polyimide bond is formed. This results in inhibition of the resonant effect of the polyimide, thereby further increasing instability.
• the thermal decomposition onset temperature around 500° C. seems to be mainly attributed to this DAT factor.
• the carboxyl group is away from the amino group and does not cause steric distortion of the polyimide.
• the polyimide is stabilized by the resonant effect.
• the weight loss around 450° C. may be attributed to this carboxyl group.
• the polyimide has the “Upilex” type structure, and seems to show a high thermal decomposition onset temperature.
• A-1 They consist of PMDA-DADE-BPDA-DAT or PMDA-DADE-BTDA-DAT (or DABz in place of DAT) copolymers soluble in solvents.
• A-2 They are obtained by direct imidation by acid-catalyzed dehydration-polycondensation reaction.
• A-3 They are synthesized via 6,6-imide segments synthesized by a three-step polycondensation reaction.
• reaction can be performed in 0.1% aqueous solvents and the endpoint of the reaction is determined by molecular weight analysis by GPC with high reproducibility.
• the imide copolymers rapidly form films at lower temperatures.
• the films show T m >500° C., and T g cannot be observed in a range up to 430° C.
• A-6 They can be modified by partially changing components.
• the polyimide copolymers are stable at room temperature for a long period so that they have good storage stability.
• B-2 Precursor polyamic acids are synthesized by addition polymerization at low temperatures in anhydrous solvents.
• polyimides are produced by heating/dehydration reaction of the polyamic acids. Polyamic acids readily decompose in water.
• Tm Thermal decomposition onset temperature
• Glass transition temperature (Tg) was measured using DSC Perkin Elmer PYRIS Diameter DSC by heating to 400° C. at a rate of 10° C./min, then air-cooling and heating again to 430° C. at a rate of 10° C./min.
• a three-necked separable glass flask equipped with a stainless steel anchor stirrer was connected to an Allihn condenser bearing a water trap.
• the flask was heated in a silicone oil bath with stirring under a stream of nitrogen gas.
• the three-necked separable flask was charged with 5.88 g (20 mmol) of 3,4,3′,4′-biphenyltetracarboxylic dianhydride (hereinafter referred to as BPDA), 8.01 g (40 mmol) of 4,4′-diaminodiphenyl ether (hereinafter referred to as DADE), 1.5 g (15 mmol) of ⁇ -valerolactone, 3.5 g (44 mmol) of pyridine, 150 g of N-methylpyrrolidone (hereinafter referred to as NMP), and 45 g of toluene.
• BPDA 3,4,3′,4′-biphenyltetracarboxylic dianhydride
• DADE 4,4′-diaminodiphenyl ether
• NMP N-methylpyrrolidone
• the flask was air-cooled with stirring at 180 rpm for 1 hour. Then, 17.45 g (80 mmol) of pyromellitic dianhydride (hereinafter referred to as PMDA), 4.88 g (40 mmol) of diaminotoluene (hereinafter referred to as DAT) and 250 g of NMP were successively added, and the flask was stirred at 180 rpm at room temperature for 20 minutes under nitrogen.
• PMDA pyromellitic dianhydride
• DAT diaminotoluene
• Tm decomposition onset temperature
• Tg glass transition temperature
• the title polyimide copolymer was synthesized in the same manner as described in Example 1.
• a flask was charged with 2.9 g (10 mmol) of BPDA, 4.00 g (20 mmol) of DADE, 1.5 g of ⁇ -valerolactone, 2.8 g of pyridine, 100 g of NMP, and 35 g of toluene.
• the flask was stirred at 180 rpm in a silicone bath at 180° C. for 1 hour under a stream of nitrogen gas.
• the silicone bath was removed and the flask was air-cooled for 30 minutes, after which 8.73 g (40 mmol) of PMDA, and 2.44 g (20 mmol) of DAT were added followed by 75 g of NMP, and the mixture was stirred at room temperature for 20 minutes.
• Tm was 506.6° C.
• Tg was not observed in a test range up to 430° C.
• a reactor was charged with 5.88 g (20 mmol) of BPDA, 8.00 g (40 mmol) of DADE, 1.5 g of ⁇ -valerolactone, 3.0 g of pyridine, 150 g of NMP, and 30 g of toluene.
• the reactor was heated in a silicone bath at 180° C. with stirring at 180 rpm for 1 hour. After air-cooling for 30 minutes, 13.10 g (60 mmol) of PMDA and 100 g of NMP were added, and the mixture was stirred at 180 rpm at room temperature, after which 5.88 g (20 mmol) of BPDA, 7.32 g (60 mmol) of DAT and 112 g of NMP were added. The mixture was stirred at room temperature for 30 minutes and then heated at 180° C. with stirring at 180 rpm for 4 hours and 35 minutes to give a solution of the title polyimide having a concentration of 10%.
• reaction solution was diluted with dimethylformamide and analyzed by GPC, but the molecular weight could not be determined.
• Tm thermal decomposition onset temperature
• Example 2 A procedure similar to that of Example 1 was performed except that benzophenone tetracarboxylic dianhydride (BTDA) was used in place of BPDA.
• BTDA benzophenone tetracarboxylic dianhydride
• a three-necked separable glass flask equipped with a stainless steel anchor stirrer was connected to an Allihn condenser bearing a water trap.
• the flask was heated in a silicone oil bath with stirring under a stream of nitrogen gas.
• the flask was charged with 6.44 g (20 mmol) of BTDA, 8.0 g (40 mmol) of DADE, 1.8 g of ⁇ -valerolactone, 3.2 g of pyridine, 150 g of NPM, and 52 g of toluene. After stirring at 180 rpm for 30 minutes at room temperature, the reactor was heated in a silicone bath at 180° C. with stirring at 180 rpm for 1 hour.
• the silicone bath was removed and the mixture was air-cooled for 30 minutes, and then stirred with 17.44 g (80 mmol) of PMDA, 44.88 g (40 mmol) of DAT, and 100 g of NMP for 15 minutes, and then 6.44 g (20 mmol) of BTDA and 4.88 g (40 mmol) of DAT were added with stirring followed by 103 g of NMP.
• the mixture was heated at 180° C. with stirring at 180 rpm for 3 hours and 20 minutes to give a polyimide solution having a concentration of 12%.
• Tm thermal decomposition onset temperature
• Example 4 A procedure similar to that of Example 4 was performed.
• a three-necked separable flask was charged with 3.22 g (10 mmol) of BTDA, 4.00 g (20 mmol) of DADE, 0.9 g of ⁇ -valerolactone, 1.8 g of pyridine, 80 g of NMP, and 30 g of toluene.
• the flask was stirred at room temperature for 30 minutes under a stream of nitrogen gas.
• the reactor was heated in a silicone bath at 180° C. with stirring at 180 rpm for 1 hour under a stream of nitrogen gas.
• the silicone bath was removed and the mixture was air-cooled for 20 minutes, and then stirred with 8.72 g (40 mmol) of PMDA, 2.44 g (20 mmol) of DAT, and 100 g of NMP at room temperature for 30 minutes, then 3.22 g (10 mmol) of BTDA, 2.18 g (10 mmol) of PMDA, 3.66 g (30 mmol) of DAT and 67 g of NMP were added and the mixture was heated at 180° C. with stirring at 180 rpm for 4 hours and 30 minutes to give a polyimide solution having a concentration of 10%.
• reaction solution A part of the reaction solution was sampled and analyzed for the molecular weight expressed as polyethylene.
• a three-necked flask was charged with 6.44 g (20 mmol) of BTDA, 8.00 g (40 mmol) of DADE, 1.5 g of ⁇ -valerolactone, 3.0 g of pyridine, 150 g of NMP, and 30 g of toluene.
• the flask was stirred at 180 rpm for 30 minutes at room temperature, and then heated at 180° C. with stirring at 180 rpm for 1 hour. Twenty ml of toluene was removed.
• the flask was air-cooled for 25 minutes, and then stirred with 13.10 g (60 mmol) of PMDA and 100 g of NMP at room temperature for 25 minutes, and 6.44 g (20 mmol) of BTDA, 7.32 g (60 mmol) of DAT, and 122 g of NMP were added, and the mixture was heated at 180° C. with stirring at 180 rpm for 4 hours and 35 minutes to give a polyimide solution having a concentration of 10%.
• reaction solution A part of the reaction solution was sampled and analyzed for molecular weight by GPC.
• a reactor was charged with 2.94 g (10 mmol) of BPDA, 4.0 g (20 mmol) of DADE, 0.9 g of ⁇ -valerolactone, 1.8 g of pyridine, 100 g of NMP, and 30 g of toluene.
• the reactor was heated at 180° C. with stirring at 180 rpm for 1 hour.
• the reactor was stirred at room temperature for 30 minutes, and then stirred with 8.72 g (40 mmol) of PMDA at 200 rpm for 30 minutes at room temperature, then with 3.04 g (20 mmol) of DABz and 83 g of NMP at 180 rpm for 1 hour.
• the film was subjected to thermal analysis by TGA-GTA.
• the temperature was raised to 600° C. at a rate of 10° C./min. A weight loss was observed at 450° C.
• the thermal decomposition onset temperature (T m ) was 544.4° C.
• a reactor was charged with 2.94 g (10 mmol) of BPDA, 4.0 g (20 mmol) of DADE, 0.9 g of ⁇ -valerolactone, 1.8 g of pyridine, 100 g of NMP, and 30 g of toluene.
• the reactor was stirred at room temperature, then heated in a silicone bath.
• the reactor was heated at 180° C. with stirring at 180 rpm for 1 hour, and air-cooled for 30 minutes.
• the mixture was stirred with 4.82 g (40 mmol) of PMDA, 2.44 g (20 mmol) of DAT, and 83 g of NMP at 180 rpm for 1 hour.
• the film was subjected to thermal analysis by TG-GTA, showing a weight loss at 445° C.
• the thermal decomposition onset temperature (T m ) was 539.5° C.
• a reactor was charged with 2.94 g (10 mmol) of BPDA, 4.0 g (20 mmol) of DADE, 1.5 g of ⁇ -valerolactone, 2.8 g of pyridine, 100 g of NMP, and 35 g of toluene.
• the reactor was stirred at room temperature, then heated in a silicone bath at 180° C. with stirring at 180 rpm for 1 hour.
• the mixture was air-cooled and then stirred with 8.73 g (40 mmol) of PMDA, 3.04 g (20 mmol) of DABz, and 75 g of NMP at room temperature for 20 minutes.
• TG-GTA analysis was performed by heating to 600° C. at a rate of 10° C./min. A weight loss was observed at 458.3° C., and the thermal decomposition onset temperature (T m ) was 553.6° C.
• Example 7 A procedure similar to that of Example 7 was performed except that benzophenone tetracarboxylic dianhydride (BTDA) was used in place of BPDA.
• BTDA benzophenone tetracarboxylic dianhydride
• a reactor was charged with 6.44 g (20 mmol) of BTDA, 8.0 g (40 mmol) of DADE, 1.8 g of ⁇ -valerolactone, 3.6 g of pyridine, 150 g of NMP, and 35 g of toluene.
• the mixture was stirred at room temperature, then heated at 180° C. with stirring at 180 rpm for 1 hour.
• the mixture was air-cooled with stirring for 30 minutes, and then stirred with 17.44 g (80 mmol) of PMDA, 6.48 g (40 mmol) of DABz, and 131 g of NMP at room temperature for 30 minutes.
• T m The thermal decomposition onset temperature
• the present invention finds a wide range of applications such as medical materials, construction materials, high-temperature members in housewares, substitutes for TeflonTM by capitalizing on the features of the new preparation process, high-performance polymers and low-cost products.

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